optoelectronic properties akin to industrial juggernauts gallium arsenide and silicon. [1,2] Yet, the materials are compatible with solution-processing techniques such as inkjet printing and spray coating. [3] This unprecedented combination has led to the development of solar cells which already show power conversion efficiencies of over 25%, similar to state-of-the-art poly-Si and other thin-film technologies, in just over 10 years of development. [4] Hybrid perovskites are particularly interesting for indoor applications, with impressive efficiencies of over 35% demonstrated under indoor illumination which may prove a viable option to power the ever expanding Internet of Things. [5] Rather than competing with the current technology giants, perovskites can work together with other solar cell technologies in a tandem configuration. Record efficiencies of over 29% for silicon-perovskite tandem solar cells have already been reported and further progress is expected in the near future. [6] Although perovskite solar cells (PSCs) are on the verge of mass production, two main challenges remain: stability [7] and toxicity. [8] Multiple reviews already address the toxicity concern, and it will not be discussed here. [9][10][11] Layered hybrid perovskites (LPKs) have emerged as an answer to battle stability concerns. Although known for decades, LPKs have only recently been incorporated in photovoltaic (PV) applications, resulting in modest device power conversion efficiencies due to poorer optoelectronic properties. [12][13][14] However, their key advantage is the stabilizing effects of the organic interlayers, which prevents perovskite degradation. [15,16] The organic spacer inhibits ion migration which prevents the formation of irreversible degradation products. [17] Alternatively, LPKs can be deposited over the state-of-the-art perovskite materials to combine the high performance of 3D perovskites with the stabilizing properties of LPKs. [15] Here, the limiting factor is inefficient charge transport across the organic interlayer, currently preventing the full exploitation of the layered structure in PSCs.This can be approached in two ways, either by keeping the LPK layer very thin, currently the most popular approach, or by increasing the electrical conductivity of the material. [18,19] The conductivity can be enhanced through increasing the number of inorganic layers n, but this comes at the price of reduced stability. [20][21][22] The better approach is to enhance the charge transport in LPKs through the molecular engineering of the organic Layered hybrid perovskites (LPKs) have emerged as a viable solution to address perovskite stability concerns and enable their implementation in wide-scale energy harvesting. Yet, although more stable, the performance of devices incorporating LPKs still lags behind that of state-of-the-art, multication perovskite materials. This is typically assigned to their poor charge transport, currently caused by the choice of cations used within the organic layer. On balance, a compromise bet...

Copper(ii) and palladium(ii) meso-tetraferrocenylporphyrins ( and ) were employed as catalysts for electrochemical proton reduction in DMF using trifluoroacetic acid (TFA) or triethylamine hydrochloride (TEAHCl) as acids. Gas analysis under electrocatalytic conditions at a glassy carbon working electrode confirmed the product as H2. showed catalytic behavior for both TFA and TEAHCl, whereas only TFA worked for . The performance of the two compounds for electrocatalytic hydrogen generation was compared to the analogous copper(ii) and palladium(ii) meso-tetraphenylporphyrins ( and ) under identical conditions. The presence of the ferrocence groups on the porphyrin favourably shift the overpotential to a less negative value by around 200 mV and increases the catalytic rate of hydrogen production in DMF/TFA by an order of magnitude to 6 × 10(3) s(-1). Moreover, while is fully inactive in a DMF/TEAHCl mixture, the ferrocene subunits activate the catalyst. Spectroelectrochemistry experiments and DFT calculations were consistent with a catalytic process proceeding via the phlorin anion.

A zinc(ii) porphyrin derivative, F3P, was prepared containing a single ferrocene group appended at three of the meso positions.